钛酸铋钠基无铅压电陶瓷研究近期进展

钛酸铋钠(分子式是Bi0.5Na0.5TiO3,简写为BNT)基无铅压电陶瓷性能优良,但与铅基陶瓷相比还有相当的差距,其性能有待进一步提高.从BNT基陶瓷改性、陶瓷新体系以及陶瓷制备技术等多方面,分析了提高BNT基陶瓷性能的原理、途径和方法,指出了发明陶瓷新体系的有关思路,讨论了陶瓷制备技术与陶瓷性能的关系.同时,列举了近期在BNT基陶瓷性能改善研究中的若干新进展和新结果、性能良好的BNT基陶瓷新体系及制备工艺和制备新技术对陶瓷性能的影响,并对今后的相关研究进行了展望.     

Interaction of Zn and Zn–4Al,Zn–15Al (wt-%) solder alloys with aluminium

The interaction of pure zinc and Zn–4Al, Zn–15Al (wt-%) solder alloys with aluminium has been investigated. Two different experimental techniques were used: (i) the aluminium samples soldering and (ii) the holding of liquid solder alloys inside the hollow in an aluminium base. The aluminium content was determined in samples after contact with aluminium at various temperatures and various holding times. It is shown that in soldered seams and solder alloys that had been held inside the aluminium base, the content of the aluminium was higher than at the points on the liquidus line on the Zn–Al equilibrium phase diagram at the corresponding temperatures and increases along with an increase in the holding time. This was apparently due to isothermal solidification.     

Bi-Cu film deposition in aqueous solutions

The relatively uniform bismuth-copper film was electrodeposited between −15 and −20 mV in the sulfate electrolyte containing 4 mmol/L bismuth ion and 2 mmol/L copper ion. Only copper was electrodeposited at −5 mV. The dendritic bismuth-copper film was electrodeposited under −20 mV. The cathodic current became constant between −20 and −400 mV. Therefore, bismuth-copper electrodeposition changes from charge transfer controlling to diffusion controlling at −20 mV. On the other hand, the uniform bismuth-copper film was electrodeposited between −5 and −35 mV in the methanesulfonate electrolyte containing 4 mmol/L bismuth ion and 2 mmol/L copper ion. The dendritic bismuth-copper film was electrodeposited under −35 mV. The potential region for good electrodepositon in methanesulfonate electrolyte is wider than that in sulfate electrolyte. Therefore, it is easy to control electrodeposition conditions by using methanesulfonate electrolyte.     

无铅无镉无锌低镁低温透明色釉的研制

以普通着色金属氧化物为色剂，基釉为无铅无镉无锌低镁透明熔块釉，研制了系列透明色釉。其成熟温度在1050～1100℃范围，发色良好，釉面光亮，显微硬度较高，适用于精陶与炻器之间的坯体。     

Exploration on the origin of enhanced piezoelectric properties in transition-metal ion doped KNN based lead-free ceramics

In this work, we studied effects of Ni₂O₃ and Co₂O₃ doping on crystal structures, microstructures, orthorhombic and tetragonal phase transition temperature (T_o-t), and electrical properties of [Li_0.06(Na_0.57K_0.43)_0.94][Ta_0.05(Sb_0.06Nb_0.94)_0.95]O₃ (LNKTSN) lead-free ceramics. The experimental results showed that the Ni₂O₃ addition with appropriate amount could shift the T_o-t downwards to the room temperature, and thus obviously increasing the room-temperature piezoelectric coefficient (d₃₃), dielectric coefficient (ε_r) and electromechanical coupling coefficient (k_p) of the LNKTSN ceramics. These were consistent with previous experimental results obtained in Fe₂O₃ doped LNKTSN ceramics. On the contrary, Co³⁺ doping shifted continuously the T_o-t upward and deteriorated obviously piezoelectric properties of LNKTSN ceramics. Fe, Co and Ni had similar ion radii and were expected to result in the same (donor or acceptor) doping effects on electrical properties of LNKTSN ceramics. The different doping effects between Co³⁺ (deterioration) and Ni³⁺ or Fe³⁺ (improvement) on the electrical properties of LNKTSN ceramics suggested that the coexistence of orthorhombic and tetragonal phases at room temperature due to downward shift of T_o-t, rather than ion doping (donor or acceptor doping) effects was the main cause for enhanced room-temperature piezoelectric properties. This conclusion can be extended to all KNN-based materials in general, thus offering principle guide for future development of new lead-free materials with good piezoelectric properties.     

Influence of Zn2+ doping on the morphotropic phase boundary in lead-free piezoelectric (1 – x)Na1/2Bi1/2TiO3-xBaTiO3

A series of morphotropic phase boundary (MPB) compositions of (1–x)Na_1/2Bi_1/2TiO₃-xBaTiO₃ (x = 0.05, 0.055, 0.06, 0.065, 0.07), with and without 0.5 mol% Zn-doping was synthesized using the solid-state route. The samples were characterized using X-ray diffraction, dielectric analysis, and electromechanical measurements (piezoelectric d₃₃ coefficient, coupling factor k_p, mechanical quality factor Q_m, and internal bias field E_bias). The increase in the ferroelectric-relaxor transition temperature upon Zn-doping was accompanied by a shift of the MPB toward the Na_1/2Bi_1/2TiO₃-rich side of the phase diagram. Higher tetragonal phase fraction and increased tetragonal distortion were noted for Zn-doped (1 – x)Na_1/2Bi_1/2TiO₃-xBaTiO₃. In addition, ferroelectric hardening and the presence of an internal bias field (E_bias) were observed for all doped compositions. The piezoelectric constant d₃₃ and the coupling coefficient k_p decreased by up to ∼30%, while a 4- to 6-fold increase in Q_m was observed for the doped compositions. Apart from establishing a structure–property correlation, these results highlight the chemically induced shift of the phase diagram upon doping, which is a crucial factor in material selection for optimal performance and commercialization.     

Creep behavior of eutectic Sn-Cu lead-free solder alloy

Tensile creep behavior of precipitation-strengthened, tin-based eutectic Sn-0.7Cu alloy was investigated at three temperatures ranging from 303–393 K. The steady-state creep rates cover six orders of magnitude (10⁻³−10⁻⁸ s⁻¹) under the stress range of σ/E=10⁻⁴−10⁻³. The initial microstructure reveals that the intermetallic compound Cu₆Sn₅ is finely dispersed in the matrix of β-Sn. By incorporating a threshold stress, σ _th, into the analysis, the creep data of eutectic Sn-Cu at all temperatures can be fitted by a single straight line with a slope of 7 after normalizing the steady-state creep rate and the effective stress, indicating that the creep rates are controlled by the dislocation-pipe diffusion in the tin matrix. So the steady-state creep rate, , can be expressed as exp , where Q_c is the activation energy for creep, G is the temperature-dependent shear modulus, b is the Burgers vector, R is the universal gas constant, T is the temperature, σ is the applied stress, A is a material-dependent constant, and , in which σ _OB is the Orowan bowing stress, and k_R is the relaxation factor. An erratum to this article is available at .     

Numerical prediction of fraction of eutectic phase in Sn−Ag−Cu soldring using the phase-field method

A combination of macroscale solidification simulation and phase-field calculation is employed to predict the volume fraction of the eutectic phase in Sn-4.0 mass% Ag-XCu solder alloys (X=0.5–1.1 mass%). The solidification simulation incorporates the cooling rate in the phase-field simulation. We assume the residual liquid solidifies as eutectic phase when the driving force for the nucleation of Cu₆Sn₅ amounts to a critical value, which is determined based on the experimental data. Though the calculation results depend on the experimental data, the obtained fractions are about 40% for 0.5 mass% Cu and more than 90% for 1.1 mass% Cu alloy, which shows good agreement with the experimental data.     

无铅压电陶瓷的器件应用分析

随着社会可持续发展战略的实施和人们环保意识的加强,无铅压电陶瓷及其器件应用已成为当前铁电压电材料及其应用研究的热点之一。该文通过对近期铋层状结构和Bi1/2Na1/2TiO3基无铅压电陶瓷,以及研发的无铅压电陶瓷的相关压电参数的分析,对照传统PZT基压电陶瓷的器件应用,分析了无铅压电陶瓷相关性能参数对器件应用的影响。     

BNKLT无铅压电陶瓷中频滤波器的研制

采用本组发明的[Bi0.5(Na1-x-yKxLiy)0.5]TiO3(BNKLT)系无铅压电陶瓷,研制了单片式中频陶瓷滤波器。该体系陶瓷具有较高的使用温度,在160℃以上仍具有较强压电性。利用此体系材料,采用轮廓振动模式,制作了插损约为3 dB,中心频率约为530 kHz,带宽约为8.8 kHz,左、右选择性均良好的无铅压电陶瓷单片式中频滤波器。除中心频率以外,各项指标均与村田公司同类含铅陶瓷中频滤波器(SFU系列)产品相当,具有良好的应用前景。